CN205676426U - A kind of device of liquid hydrocarbon fine de-sulfur - Google Patents
A kind of device of liquid hydrocarbon fine de-sulfur Download PDFInfo
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- CN205676426U CN205676426U CN201620613483.7U CN201620613483U CN205676426U CN 205676426 U CN205676426 U CN 205676426U CN 201620613483 U CN201620613483 U CN 201620613483U CN 205676426 U CN205676426 U CN 205676426U
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Abstract
The utility model discloses the device of a kind of liquid hydrocarbon fine de-sulfur, it amine eluting hydrogen sulfide unit including adding the hydrogen sulfide in MDEA lean amine absorption liquid hydrocarbon, add rich carbonyl sulfide removal agent liquid hydrocarbon carries out the carbonyl sulfide hydrolysis of decarbonylation base sulphuring treatment and absorbs hydrogen sulfide unit, add regeneration alkali liquor and liquid hydrocarbon is carried out the caustic wash desulfuration alcohol unit of de-disulfide, liquid hydrocarbon carries out washing the washing dealkalize unit of dealkalize, the extractive distillation disulfide unit of the disulfide in removing liquid hydrocarbon and the adsorbent desulfurization unit of the liquid hydrocarbon after extractive distillation desulfurization, pending liquid hydrocarbon flows through said apparatus successively；Have an advantage in that: 1) for liquid hydrocarbons such as the liquefied gas containing different morphologic sulphur, carbon three, carbon four, carbon five, use MDEA amine liquid and fiber film contactor extracting removing hydrogen sulfide, hydrogen sulfide stripping rate is more than 99.9%；2) use described complete desulfurization process, total sulfur in liquid hydrocarbon can be removed to below 1ppm.
Description
Technical field
This utility model relates to a kind of opening for liquid hydrocarbons such as the liquefied gas containing different morphologic sulphur, carbon three, carbon four, carbon five
The chemical industry equipment sent out, the device of a kind of liquid hydrocarbon fine de-sulfur.
Background technology
Along with the in poor quality of crude oil and high-sulfurized, the liquefied gas of oil refining enterprise's processing crude oil production and fraction products such as carbon thereof
Three, in the liquid hydrocarbon such as carbon four, carbon five, sulfur content is more and more higher, and sulfur speciation becomes increasingly complex, and carrying along with living standard
Height, people are more and more higher to the requirement of petrochemicals and living environment, oil refining enterprise also update production technology and
Product desulfurization technology is to meet above-mentioned production, life requirement.
Find according to the investigation of above-mentioned liquid hydrocarbon process units, the catalytic liquid activating QI that major part enterprise or device produce
Based on hydrogen sulfide and mercaptan, cos, thioether and disulfide content are few, the generally mg/Nm of units3, even survey not
Go out；In the catalytic liquid activating QI that small part enterprise or device produce, cos, thioether and disulfide content are higher, after some time it is possible to reach ten
The mg/Nm of number3；And in the coking liquefied gas that overwhelming majority enterprise or device produce cos, thioether and disulfide content is the most relatively
Catalytic liquid activating QI is the most higher, cos, thioether and disulfide content in the coking liquefied gas that small part enterprise or device produce
Then can exceed that 100mg/Nm3, there is disulfide content more than 1000 mg/Nm in individual device3Operating mode.
Carbon three, carbon four, the fractional distillation component of carbon five generally liquefied gas, or be the pyrolysis product of Petroleum, its sulfur content
And fractions distribution is directly related with the sulfur content of raw material and fractions distribution.
For the hydrogen sulfide in liquid hydrocarbon, what employing was most at present is N methyldiethanol amine aqueous solution extraction process, inhales
After receiving hydrogen sulfide, amine liquid uses heating analytic technique to regenerate, and sulfide hydrogen sour gas enters sulphur unit and produces sulfur；As long as
Amine liquid extraction tower and regenerator design correctly and press workbook normal operating, and the hydrogen sulfide content in de-rear liquid hydrocarbon is mostly
Can reach to design requirement；The side of hydrogen sulfide in patent 201210269574.X liquid film absorption tower amine absorption removing liquefied gas
Method, and liquefied gas enters by 201520069733.0 1 kinds of liquid film reactor amine absorption depriving hydrogen sulphides of patent and alkali liquor removal of mercaptans
The method of row desulfurization, is all the use of this principle；The patent 201520951883.4 of the applicant relates to a kind of fiber liquid film
The method of catalyst amine eluting hydrogen sulfide, relatively above-mentioned two patent has bigger technological improvement.
For the cos in liquid hydrocarbon, current existing technology is room temperature or the low temperature hydrolysis catalyst of solid, by carbonyl
Base sulfur is hydrolyzed to hydrogen sulfide and carbon dioxide, then uses the adsorbent removing hydrogen sulfide such as zinc oxide；This technology requires in liquid hydrocarbon
Water content can not be too high, and general requirement is less than 100ppm, it is therefore desirable to design solid caustic soda tower or molecular sieve tower dehydration facility；With
Time, being limited by solid hydrolyst and hydrogen sulfide adsorbent Sulfur capacity, COS content is the highest, and service life is the shortest, after inefficacy
Solid waste needs landfill disposal, forms secondary pollution；It addition, carbonyl sulfide hydrolysis and absorption depriving hydrogen sulphide need to control suitable air speed,
Otherwise desulfuration efficiency declines, and therefore, utilizes the feature that cos is close with propylene boiling point, and de-cos is typically designed at liquefied gas
Polypropylene plant after gas separation unit；In sum, plant investment and the desulphurization cost of this type of technology are higher；Patent
200510012331, patent 200410074539.8, patent 101108339, patent 1340373, patent 201410218662.6
Described is all solid hydrolyst.
The patent 201610256212.5 of the applicant and patent 201610256214.4 relate to a kind of liquid carbonyl sulfur water
Solving catalyst and the method for removing cos thereof, hydrolytic catalyst of carbonyl sulfur is one or more organic amines and one or more phases
Transfer catalyst and the liquid phase mixture of one or more Cobalt Phthalocyanine class catalyst, use two-stage fiber film contactor to take out
Carrying, the first order uses liquid carbonyl sulfide hydrolysis to be hydrogen sulfide and carbon dioxide by the carbonyl sulfide hydrolysis in liquid hydrocarbon, the
Two grades use MDEA amine absorption, and in rich amine solution delivers to factory, amine liquid regenerative system regenerates.
The patent 201610256215.9 of the applicant, patent 201610256192.1 and patent 201620347339.3,
It is that the liquid carbonyl sulfide hydrolysis described in patent 201610256212.5 is mixed with sodium hydroxide lye, uses one-level fine
Cos in dimension liquid membrane contactor extracting removing liquid hydrocarbon.
For the mercaptan in liquid hydrocarbon, what employing was most at present is MEROX technique, sodium hydroxide in this technology utilization alkali liquor
Sodium mercaptides is generated with thiol reactant, containing sodium mercaptides alkali liquor under the catalyst actions such as sulfonation titanium cyanines cobalt, anti-with the oxygen in air
Should generate sodium hydroxide and disulfide, old technique takes away disulfide by the way of tail gas is carried secretly and frequently changed alkali liquor, and nearly ten
Technology for many years uses gasoline equal solvent back suction to put forward removing disulfide, or separation and recovery disulfide technology, and alkali liquor changes the frequency
Older technique is greatly decreased；Alkali liquor after removing disulfide is regenerated, and can recycle with long period；But due to different manufacturers
Technology is variant, and removing disulfide efficiency is the most different, still has on a small quantity or trace disulfide is stripped in regeneration alkali liquor
In refined liquid hydrocarbon, liquid hydrocarbon total sulfur is caused to raise.
Patent 200710071004.9 relates to the oxidized regenerating method of a kind of liquid gas sweetening alkali liquor, liquid gas sweetening
Alkali liquor low discharge deoxidation, under catalyst action, oxygen-enriched air passes through gas distributor with microvesicle formal distribution at oxidizing tower
In interior alkali liquor, the disulfide of alkali liquor oxidized generation floats over alkali liquor upper strata and strains separation and recovery by inclining, after the regeneration of this partial oxidation
Alkali liquor is used for liquid gas sweetening with unoxidized alkali liquor mixing Posterior circle.
Patent 200710308071.8 relates to the segregation apparatus of a kind of oil-containing alkali liquor, is in patent 200710071004.9 institute
The basis transformation of the alkali liquor oxidized tower stated, oxidizing tower is being divided into Liang Ge district, left and right longitudinally through increase dividing plate, zoneofoxidation is tied
Structure is identical with microvesicle oxidation technology described in patent 200710071004.9；The upper end in twoth district connects so that alkali liquor is from oxidation after Yang Hua
District overflows across dividing plate and flows to Disengagement zone, and under the coalescent pack effect of Disengagement zone, the disulfide that oxidation generates divides with alkali liquor in Disengagement zone
Layer also rests on upper strata, and periodic exhaustion disulfide goes out to aoxidize knockout tower；Do not separate disulfide thoroughly and pass through air or nitrogen again
Air stripping takes in tail gas, thus realizes alkali liquid regeneration.
Patent 201220012653.8 relates to the combined system of a kind of liquid gas sweetening, and desulfuration of liquefied gas alcohol moiety uses
Liquid film reactor caustic wash desulfuration alcohol described in patent 201520069733.0, removal of mercaptans alkali liquor uses patent 200710308071.8
The oxidation of described alkali liquor microvesicle, coarse separation are reclaimed and air stripping removing disulfide technology regenerates.
Patent 201210276509.x relates to a kind of gasoline light fraction removal of mercaptans and the method for alkali liquid regeneration, light for gasoline
The mercaptan of fraction, uses liquid film reactor caustic wash desulfuration alcohol, and after removal of mercaptans, alkali liquor uses alkali described in patent 200710308071.8
Liquid oxidation and separation disulfide technology, then use low sulfur naphtha liquid film back suction to carry the disulfide of removing residual, so that alkali liquor
Regenerated.
Patent 201220253818.0 relates to a kind of catalytic liquid activating QI deep desulfuration alcohol device, uses three grades of fiber liquid films anti-
Answering device caustic wash desulfuration alcohol, removal of mercaptans alkali liquor uses conventional fillers oxidizing tower to aoxidize with air under catalyst existence condition,
The disulfide generated uses two-stage fiber liquid film reactor and the anti-extraction technique of solvent to remove, and after regeneration, alkali liquor is used for liquefying
Gas circulation desulfurization alcohol.
The patent 201420514825.0 of the applicant, patent 201410454906.0 and patent 201520325634.4 relate to
And mercaptan oxidation and alkali liquor oxidized regeneration method, mercaptan oxidation uses fibrous membrane alkali cleaning extracting, and removal of mercaptans alkali liquor uses
It is different from alkali liquor and the feeding manner of air downflow type of above-mentioned alkali liquor oxidized regeneration Patents, but uses adverse current feeding side
Formula, the alkali liquor liquid distribution trough from oxidizing tower top enters, and air enters from the gas distributor of tower bottom；Top of tower is provided with parent
Water packing separates from the disulfide being layered to accelerate alkali liquor, and tower top is provided with L-type dividing plate, in order to reclaim two sulfur of layering
Ether, tower bottom is provided with lipophile filler and removes the disulfide of residual in alkali liquor with further, is distributed at liquid distributor and gas
Anti-whirlpool internals it are also devised with between device, disturbance during to alleviate alkali liquor oxidized and disulfide emulsifying, from the alkali liquor sent at the bottom of tower again
Using gasoline or the disulfide of Petroleum fibrous membrane extracting removing residual further, after regeneration, alkali liquor is used for oil product circulation desulfurization
Alcohol.
For the disulfide in liquid hydrocarbon, and the disulfide that removal of mercaptans alkali liquid regeneration is stripped in liquid hydrocarbon, currently
The report of commercial Application is less.
Patent 00129724.4 proposes one and mercaptan in liquefied gas is first converted into disulfide, then uses distillation technique to remove
Disulfide, the method finally mixture of tower bed material disulfide and liquefied gas heavy constituent being carried out rectification and purification again.
The patent 201510020582.4 of the applicant relate in a kind of extractive distillation removing methyl tertiary butyl ether(MTBE) MTBE with
Disulfide is main desulfurizing agent, and the MTBE mid-boiling point most Sulfurs higher than MTBE can be extracted into desulfurization by abstraction desulfurization agent
In agent, then by distillation technique, MTBE and sulfur-bearing abstraction desulfurization agent are separated, thus realize the purpose of desulfurization；Extract simultaneously
Desulfurizing agent can also significantly alleviate base product and reboiler coking, extension device time between overhauls(TBO) and service life.
For the thioether in liquid hydrocarbon, because thioether content is extremely low, also it is not apparent from affecting product quality, does not causes weight at present
Depending on, research papers or patent there are no report；The applicant's Patents relates to the Patent No. of fiber film contactor
201520686490.5。
Patent 200910250279.8 relate to a kind of can the liquid hydrocarbon mercaptan removal technique of deeply removing total sulfur, this technology is passing
During the liquid hydrocarbon of system extracts and be alkali liquor oxidized, improve extraction efficiency by adding auxiliary agent in extracting alkali liquor, strengthen alkali liquor
Oxidation and solvent back suction propose the measures such as three-phase degree of mixing, regenerating alkali liquid oxidation catalyst, circulation alkali liquor deoxidation, improve Mercaptan removal
The degree of depth, also can improve carbonyl sulfide removal rate simultaneously, reduce the disulphide impact on liquefied refinery gas of alkali liquor oxidized generation.
Patent 201010562891.1 relates to the process for purification of a kind of liquefied gas, and employing solid carbonyl sulfide hydrolysis will
Carbonyl sulfide hydrolysis is hydrogen sulfide, then uses alkanolamine solution Absorption Desulfurization hydrogen, and after de-cos, liquefied gas uses removal of mercaptans agent again
Extracting removing, rich removal of mercaptans agent uses steam stripping technique removing mercaptan, and removal of mercaptans agent is regenerated recycling.
Patent 01134688.4 relates to a kind of method of indudstrialized refining liquefied gas, and liquefied gas is by fixed bed reactors
Desulfurizing agent and catalyst, convert mercaptans to disulfide, liquefied gas through further rectification remove disulfide, it is achieved desulfurization
Purpose.
Patent 201410218896.0 relates to the process for purification of a kind of liquefied gas, and employing solid carbonyl sulfide hydrolysis will
Carbonyl sulfide hydrolysis is hydrogen sulfide, then uses alkanolamine solution Absorption Desulfurization hydrogen, and after de-cos, liquefied gas uses thioetherification to urge again
Mercaptan is generated, with etherification of olefine, the disulfide that boiling point is higher by agent, then uses distillation column separation liquefied gas and disulfide, it is achieved
Removing cos and the purpose of mercaptan.
In sum, above-mentioned patent is both for the liquid hydrocarbon of a certain classification, or for a certain in liquid hydrocarbon or
Two kinds of Sulfurs use corresponding desulfurization technology, it is impossible to effectively all of Sulfur in removing liquid hydrocarbon, it is impossible to meet current liquid
State hydrocarbon sulfur content raises and product quality requires increasingly harsher growth requirement.
Utility model content
This utility model is not enough for prior art, it is provided that comprehensive, can process the liquefied gas of different morphologic sulphur, carbon three,
A kind of device of the liquid hydrocarbon fine de-sulfur of the liquid hydrocarbon of the mixing such as carbon four, carbon five.
In order to solve above-mentioned technical problem, this utility model is addressed by following technical proposals: a kind of liquid hydrocarbon essence
The device of desulfurization, including amine eluting hydrogen sulfide unit, the rich carbonyl of addition of the hydrogen sulfide added in MDEA lean amine absorption liquid hydrocarbon
Base sulfur scavenger carries out the carbonyl sulfide hydrolysis of decarbonylation base sulphuring treatment and absorbs hydrogen sulfide unit, adds regeneration alkali liquor pair liquid hydrocarbon
Liquid hydrocarbon carries out the caustic wash desulfuration alcohol unit of de-disulfide, liquid hydrocarbon carries out washing the washing dealkalize unit of dealkalize, removing liquid
The extractive distillation disulfide unit of the disulfide in state hydrocarbon and the adsorbent desulfurization list of the liquid hydrocarbon after extractive distillation desulfurization
Unit, pending liquid hydrocarbon flows through said apparatus successively；Described amine eluting hydrogen sulfide unit includes that depriving hydrogen sulphide fiber liquid film connects
Tentaculum and amine liquid settlement separation tank, described depriving hydrogen sulphide fiber film contactor is circumscribed with pending liquid hydrocarbon pipe and the lean amine of MDEA
Carbonyl sulfide hydrolysis described in liquid pipe and absorption hydrogen sulfide unit include that de-cos venturi mixer, de-cos fiber liquid film connect
Tentaculum and carbonyl sulfide removal agent settlement separation tank；Described de-cos venturi mixer and described amine liquid settlement separation tank pair
Connect, and side joint have rich carbonyl sulfide removal agent pipe, the bottom of described carbonyl sulfide removal agent settlement separation tank be provided with lean cos take off
Except agent pipe；Described caustic wash desulfuration alcohol unit includes removal of mercaptans fiber film contactor and alkali liquor settlement separation tank, described removal of mercaptans
Fiber film contactor docks with described carbonyl sulfide removal agent settlement separation tank, and side joint has regeneration alkali liquor pipe；Described alkali liquor sinks
The bottom of fall knockout drum is provided with alkali liquor oxidized pipe；Described washing dealkalize unit includes that liquid hydrocarbon washes venturi mixer, liquid
State hydrocarbon washing fiber film contactor, liquid hydrocarbon washing settlement separation tank and liquid hydrocarbon washing water booster pump；Described liquid hydrocarbon water
Wash venturi mixer to dock with described alkali liquor settlement separation tank；Described extractive distillation disulfide unit includes abstraction desulfurization agent
Tank, abstraction desulfurization agent dosing pump, abstraction desulfurization agent blender, extraction distillation column, extraction distillation column liftout cooler, extractive distillation
Tower top material return tank, extraction distillation column liftout reflux pump, reboiler and extraction distillation column bed material cooler, described extraction distillation column
Equipped with column plate two, described abstraction desulfurization agent blender docks with liquid hydrocarbon washing settlement separation tank；Described adsorbent desulfurization unit
Including absorption desulfurizing tower, described absorption desulfurizing tower built with modified molecular screen, described absorption desulfurizing tower and described extraction distillation column
Liftout reflux pump docks；It is additionally provided with the carbonyl sulfide removal agent regeneration unit that rich carbonyl sulfide removal agent recycling is processed, described
Carbonyl sulfide removal agent regeneration unit includes rich carbonyl sulfide removal agent regenerator, tower top material reflux pump, tower top material return tank, tower bed material
Cooler and lean carbonyl sulfide removal agent booster pump；Described rich carbonyl sulfide removal agent regenerator built with column plate one and heating coil,
Described lean carbonyl sulfide removal agent pipe is docked on rich carbonyl sulfide removal agent regenerator, and described rich carbonyl sulfide removal agent pipe is docked at institute
State on lean carbonyl sulfide removal agent booster pump.
Also including adding the alkali liquor oxidized unit that alkali liquor is aoxidized by air, described alkali liquor oxidized unit includes that alkali liquor is pre-
Hot device, catalyst injector, air and liquid mixer and alkali liquor filler oxidizing tower；Described air and liquid mixer is circumscribed with compressed air hose,
Be disposed with gas-liquid allotter, filler and L-type dividing plate in described alkali liquor filler oxidizing tower from bottom to top, described L-type dividing plate every
Alkali liquor washing pipe it is circumscribed with at the region become；Described alkali liquor oxidized pipe, described alkali liquor preheater, described air and liquid mixer and described
Gas-liquid allotter is sequentially connected.
Also including and provide the alkali liquor back suction stripping unit of regeneration alkali liquor, described alkali liquor back suction stripping unit includes that back suction carries fiber
Liquid membrane contactor, oil alkali settlement separation tank, regenerating alkali liquid pump and solvent circulating pump, be provided with in described oil alkali settlement separation tank every
Plate；Described back suction carries fiber film contactor and docks with described alkali liquor washing pipe, described regenerating alkali liquid pump and described regeneration alkali liquor
Pipe docks.
Also including the solvent washing unit adding water to process sulfur-bearing solvent, described solvent washing unit includes aqueous solvent
Wash venturi mixer, solvent washing settlement separation tank and aqueous solvent wash water booster pump；Described solvent washing venturi mixer
Dock with described solvent circulating pump.
Described modified molecular screen is the 13x molecular sieve through rare earth element modification by calcination.
Described filler is porcelain ball, Pall ring, Raschig ring, ripple packing or wire packing；Regular windrow or scattered heap can be used
Material.
This utility model compared with prior art, has the advantages that 1) for the liquid containing different morphologic sulphur
The liquid hydrocarbons such as activating QI, carbon three, carbon four, carbon five, use MDEA amine liquid and fiber film contactor extracting removing hydrogen sulfide, hydrogen sulfide
Removal efficiency is more than 99.9%；2) use a kind of can hydrolyzing carbonyl sulfur and absorb hydrolysis generate hydrogen sulfide carbonyl sulfide removal agent and
Fiber film contactor extracting removing cos, carbonyl sulfide removal rate is more than 99%；3) sodium hydroxide lye extraction technique is used to take off
The alkali liquor carried secretly after sulphur removal alcohol, employing washing extraction technique removing alkali cleaning, Mercaptan removal rate is more than 98%, and removal of mercaptans alkali liquor uses
Filler oxidizing tower air oxidation and fiber film contactor solvent back suction carry removing disulfide, the more traditional MEROX of alkali liquid regeneration rate
Technique improves more than 80%；4) using abstraction desulfurization agent extractive distillation technology removing disulfide, disulfide takes off fall rate more than 98%；5)
Using modified molecular screen adsorbing and removing residual sulphur, residual removing is ready is more than 95%；6) described complete sulfur removal technology stream is used
Journey, can be removed to below 1ppm by total sulfur in liquid hydrocarbon.
Accompanying drawing explanation
Fig. 1 is the single unit system process chart of this utility model embodiment.
Detailed description of the invention
With detailed description of the invention, this utility model is described in further detail below in conjunction with the accompanying drawings: as it can be seen, mark
As follows: depriving hydrogen sulphide fiber film contactor 1, amine liquid settlement separation tank 2, de-cos fiber film contactor 3, cos take off
Except agent settlement separation tank 4, removal of mercaptans fiber film contactor 5, alkali liquor settlement separation tank 6, liquid hydrocarbon washing fiber liquid film contact
Device 7, liquid hydrocarbon washing settlement separation tank 8, back suction carry fiber film contactor 9, oil alkali settlement separation tank 10, dividing plate 11, decarbonylation
Base sulfur venturi mixer 12, liquid hydrocarbon washing venturi mixer 13, abstraction desulfurization agent tank 14, abstraction desulfurization agent blender
15, extraction distillation column 16, column plate 2 17, extraction distillation column liftout cooler 18, extraction distillation column liftout return tank 19, reboiler
20, extraction distillation column bed material cooler 21, absorption desulfurizing tower 22, modified molecular screen 23, rich carbonyl sulfide removal agent regenerator 24, tower
Plate 1, heating coil 26, tower top material return tank 27, tower bed material cooler 28, alkali liquor preheater 29, catalyst injector 30,
Air and liquid mixer 31, alkali liquor filler oxidizing tower 32, L-type dividing plate 33, filler 34, gas-liquid allotter 35, solvent washing venturi mixes
Clutch 36, solvent washing settlement separation tank 37, liquid hydrocarbon washing water booster pump 38, abstraction desulfurization agent dosing pump 39, extractive distillation
Tower top material reflux pump 40, lean carbonyl sulfide removal agent booster pump 41, regenerating alkali liquid pump 42, solvent circulating pump 43, aqueous solvent wash water increase
Press pump 44, tower top material reflux pump 45, pending liquid hydrocarbon pipe a1, lean amine liquid pipe a2, rich carbonyl sulfide removal agent pipe b1, lean cos
Scavenger pipe b2, regeneration alkali liquor pipe c1, alkali liquor oxidized pipe c2, compressed air hose c3, alkali liquor washing pipe c4, amine eluting hydrogen sulfide list
Unit A, carbonyl sulfide hydrolysis and absorption hydrogen sulfide unit B 1, carbonyl sulfide removal agent regeneration unit B2, caustic wash desulfuration alcohol unit C1, alkali liquor
Oxidation unit C2, alkali liquor back suction stripping unit C3, solvent washing unit C4, washing dealkalize cells D, extractive distillation disulfide unit E,
Adsorbent desulfurization unit F.
The device of a kind of liquid hydrocarbon fine de-sulfur, including following several functional device modules: 1 adds MDEA lean amine liquid is used for inhaling
Receive the amine eluting hydrogen sulfide unit A of hydrogen sulfide in liquid hydrocarbon, the 2 rich carbonyl sulfide removal agent of addition carry out de-cos to liquid hydrocarbon
The carbonyl sulfide removal agent that rich carbonyl sulfide removal agent recycling is processed by the carbonyl sulfide hydrolysis processed and absorption hydrogen sulfide unit B 1,3
Regeneration unit B2,4 add regeneration alkali liquor carries out the de-caustic wash desulfuration alcohol unit C1 of disulfide, 5 addition air to alkali to liquid hydrocarbon
Alkali liquor oxidized unit C2 that liquid carries out aoxidizing, 6 provide regeneration alkali liquor back suction stripping unit C3 of alkali liquor, 7 add water to process sulfur-bearing
The solvent washing unit C4 of solvent, 8 liquid hydrocarbon carried out washes dealkalize wash two sulfur in dealkalize cells D, 9 removing liquid hydrocarbons
The extractive distillation disulfide unit E of ether, the adsorbent desulfurization unit F of 10 liquid hydrocarbons after extractive distillation desulfurization.
Amine eluting hydrogen sulfide unit A includes depriving hydrogen sulphide fiber film contactor 1 and amine liquid settlement separation tank 2, devulcanization
Hydrogen fiber film contactor 1 is circumscribed with pending liquid hydrocarbon pipe a1 and MDEA lean amine liquid pipe a2；Pending liquid hydrocarbon is at pressure 0.5
～in the range of 2.5MPa, temperature 10～60 DEG C, under pressure itself effect, flow into pending liquid hydrocarbon pipe a1, amine liquid lean with MDEA
Flow in depriving hydrogen sulphide fiber film contactor 1 after MDEA lean amine liquid mixing in pipe a2 and react, the lean amine absorption of MDEA
Become rich amine solution after hydrogen sulfide in pending liquid hydrocarbon to flow out；The amine liquid regenerative system regeneration that rich amine solution is conveyed to outside device
Become lean amine liquid；One or more levels depriving hydrogen sulphide fiber film contactor can be designed according to hydrogen sulfide content situation in liquid hydrocarbon,
Hydrogen sulfide content is less than 10000mg/Nm3Operating mode, be typically designed first grade desulfurizing hydrogen fiber film contactor, hydrogen sulfide can take off
Remove to 10mg/Nm3Below；This portion of techniques patent applied for 201520951883.4.
Depriving hydrogen sulphide fiber film contactor 1 inner core filament surface processes through hydrophilic modifying, makes the hydrolysis of polarity urge
Agent forms micron-sized thin film at its face extensions, and nonpolar liquid hydrocarbon is disperseed by a large amount of cellosilks in equipment inner core
Becoming oil phase thin film, biphase with the contact of membrane-membrane form, packed tower or plate column that contact area is more conventional increase thousands of times；Liquid
Cos in hydrocarbon contacts fully with the catalyst in aqueous phase, significantly improves hydrolysis rate and the degree of depth of cos；Meanwhile,
Oil, water are biphase to be contacted as Laminar Flow with membrane-membrane form, and biphase disturbance is minimum, significantly reduces two alternate mutual emulsifyings, has
It is beneficial to the most biphase quickly be completely separated in settling tank；Apply for as entitled " a kind of tencel liquid film reactor ", the patent No.
It it is the utility patent of 201520686490.5.
Carbonyl sulfide hydrolysis and absorption hydrogen sulfide unit B 1 include de-cos venturi mixer 12, de-cos fiber liquid
Membrane contactor 3 and carbonyl sulfide removal agent settlement separation tank 4, de-cos venturi mixer 12 and amine eluting hydrogen sulfide unit A
Docking, and side joint has rich carbonyl sulfide removal agent pipe b1, the bottom of carbonyl sulfide removal agent settlement separation tank 4 is provided with lean cos and takes off
Except agent pipe b2.
The liquid hydrocarbon flowed out from amine liquid settlement separation tank 2 takes off with the cos flowed out from rich carbonyl sulfide removal agent pipe b1
It is fully contacted in entering decarbonylation base sulfur fiber film contactor 3 except agent after mixing in de-cos venturi mixer 12, liquid
Carbonyl sulfide hydrolysis in state hydrocarbon is hydrogen sulfide and carbon dioxide, and hydrogen sulfide and amine eluting hydrogen sulfide unit A that hydrolysis generates carry secretly
The hydrogen sulfide entered is attracted in carbonyl sulfide removal agent, and liquid hydrocarbon separates in settlement separation tank with rich carbonyl sulfide removal agent；This
The carbonyl sulfide removal agent used during individual step is poly-is described in application number 201610256212.5.
Carbonyl sulfide removal agent regeneration unit B2 includes rich carbonyl sulfide removal agent regenerator 24, tower top material reflux pump 45, tower top
Material return tank 27, tower bed material cooler 28 and lean carbonyl sulfide removal agent booster pump 41；Rich carbonyl sulfide removal agent regenerator 24 is built-in
There are column plate 1 and heating coil 26.
From lean carbonyl sulfide removal agent pipe b2, flow out low discharge carbonyl sulfide removal agent enter rich carbonyl sulfide removal agent regenerator
24, in heating coil 26, distillation heat is to 115-125 DEG C of scope, operates pressure 0.1-0.2MPa, hydrogen sulfide and cos
Scavenger resolves, and carbonyl sulfide removal agent is transferred to lean dose by rich agent, after flowing into the condensation of tower bed material cooler 28, then is taken off by lean cos
Except agent booster pump 41 is reused in rich carbonyl sulfide removal agent pipe b1 enters carbonyl sulfide removal agent settlement separation tank 4；This
Sample, carbonyl sulfide removal agent is reused, it is ensured that carbonyl sulfide removal agent maintains higher desulfurization level.
The hydrogen sulfide gas of the gaseous state parsed and the carbonyl sulfide removal agent carried secretly are from rich carbonyl sulfide removal agent regenerator 24
End enter in tower top material return tank 27, hydrogen sulfide gas therein is sent to and is made acid tail gas and process or recycle, and carries secretly
Carbonyl sulfide removal agent be again introduced into rich carbonyl sulfide removal agent regenerator 24 by tower top material reflux pump 45.
In general, in liquid hydrocarbon, COS content is less than 100mg/Nm3, cos fiber liquid can be taken off through one-level
Membrane contactor, can be removed to below 1mg/Nm3；For the operating mode that COS content is higher, two-stage or multistage decarbonylation base can be designed
Sulfur fiber film contactor, the hydrogen sulfide content in liquid hydrocarbon also can be controlled in 1mg/Nm3Below.
Caustic wash desulfuration alcohol unit C1 includes removal of mercaptans fiber film contactor 5 and alkali liquor settlement separation tank 6, removal of mercaptans fiber
Liquid membrane contactor 5 docks with carbonyl sulfide hydrolysis and absorption hydrogen sulfide unit B 1, and side joint has regeneration alkali liquor pipe c1；Alkali liquor sedimentation point
Alkali liquor oxidized pipe c2 it is provided with from the bottom of tank 6；From carbonyl sulfide hydrolysis and absorbing hydrogen sulfide unit B 1 flows out liquid hydrocarbon with from
The regeneration alkali liquor that regeneration alkali liquor pipe c1 flows out carries out haptoreaction, the sulfur in liquid hydrocarbon in removal of mercaptans fiber film contactor 5
Alcohol and the sodium hydroxide in alkali liquor react generation sodium mercaptides, and reacted liquid hydrocarbon enters from the upper end of removal of mercaptans settlement separation tank
Washing dealkalize cells D, the alkali liquor containing sodium mercaptides enters alkali liquor oxidized unit C2 from alkali liquor oxidized pipe c2.
Alkali liquor oxidized unit C2 includes alkali liquor preheater 29, catalyst injector 30, air and liquid mixer 31 and alkali liquor filler
Oxidizing tower 32；Air and liquid mixer 31 is circumscribed with compressed air hose c3, is disposed with from bottom to top in alkali liquor filler oxidizing tower 32
Gas-liquid allotter 35, filler 34 and L-type dividing plate 33, be circumscribed with alkali liquor washing pipe c4 at the region that L-type dividing plate 33 is divided into；From alkali liquor
The alkali liquor containing sodium mercaptides flowed out in oxidation tube c2 flows through alkali liquor preheater 29, catalyst injector 30 and gas-liquid mixed successively
Device 31 enters the inside of alkali liquor filler oxidizing tower 32, it is also possible to be carried over making other use.
Operation Stress control in alkali liquor preheater 29 is in 0.1-0.6MPa scope, and optimal performance pressure is 0.3-
0.4MPa；The alkali liquor oxidized catalyst made equipped with sulfonation titanium cyanines cobalt or titanium cyanines cobalt ichthyodin in catalyst injector 30, alkali liquor
Middle catalyst optium concentration is in 100-200ppm scope；Alkali liquor oxidized temperature in alkali liquor filler oxidizing tower 32 controls at 30-65
DEG C scope, optimum temperature is 45-55 DEG C.
The gas-liquid mixture that the alkali liquor containing sodium mercaptides after preheating produces after mixing with compressed air, at gas-liquid allotter 35
Even action is distributed on each cross section of alkali liquor filler oxidizing tower；Heap is put or dissipated to filler 34 for regular, and filler can be optional
Porcelain ball, Pall ring, Raschig ring, ripple packing and wire packing etc., preferentially select ripple packing；Gas-liquid mixture enters one through filler
Step is cut into droplet and minute bubbles, biphase is fully contacted, and under alkali liquor oxidized catalyst action, sodium mercaptides is oxidized to hydroxide
Sodium and disulfide, disulfide density is little compared with alkali liquor, floats on alkali liquor upper strata, overflows across L-type dividing plate 33, L-type dividing plate 33 together with alkali liquor
Act as gas-liquid separation, liquid enters alkali liquor back suction stripping unit C3, and gas is discharged into vent gas treatment link from top.
Alkali liquor back suction stripping unit C3 includes that back suction carries fiber film contactor 9, oil alkali settlement separation tank 10, regenerating alkali liquid pump
42 and solvent circulating pump 43, it is provided with dividing plate 11 in oil alkali settlement separation tank 10；Alkali liquor containing disulfide enters with circulating solvent
In back suction carries fiber film contactor 9 and be fully contacted, separation in oil alkali settlement separation tank 10, disulfide is extracted to solvent
In, the alkali liquor after removing disulfide is referred to as regenerating alkali liquor, in regenerating alkali liquid pump sent for regeneration alkali liquor pipe c1；Fraction generates
Sulfur-bearing solvent fraction enters solvent washing unit C4 through solvent circulating pump 43 after overflowing dividing plate 11.
Solvent washing unit C4 includes solvent washing venturi mixer 36, solvent washing settlement separation tank 37 and aqueous solvent
Wash water booster pump 44；Sulfur-bearing solvent fraction sends to washing dealkalize, supplements the low-sulfur solvent waiting flow simultaneously, contains with other parts
Sulfur solvent is mixed into circulating solvent, and the sulfur-bearing solvent of fraction mixes through washing venturi mixer 36 with demineralized water or softening water
Closing, in the alkali dose carried secretly to washing water, the two separates at solvent washing settlement separation tank 37, and alkaline water periodic exhaustion goes out dress
Putting, supplement the fresh demineralized water of equivalent simultaneously or soften water, supplementary fresh water is sent into solvent by aqueous solvent wash water booster pump 44
Washing settlement separation tank 37；Alkali liquor oxidized tower is typically designed one, and in regeneration alkali liquor, sodium mercaptides content can reach below 100ppm；
Back suction carries fiber film contactor can design one-level or two-stage, and solvent washing design one-level, in regeneration alkali liquor, disulfide contains
Amount can be controlled in below 100ppm, and sulfur-bearing solvent neutral and alkali material can be controlled in below 1ppm；Can contain according to mercaptan in liquid hydrocarbon
Amount design removal of mercaptans fiber liquid film contact is one or more levels, and in catalytic liquid activating QI, mercaptan can be removed to 2mg/Nm3Hereinafter, coking
In liquefied gas, mercaptan can be removed to 10mg/Nm3Below.
Washing dealkalize cells D include liquid hydrocarbon washing venturi mixer 13, liquid hydrocarbon washing fiber film contactor 7,
Liquid hydrocarbon washing settlement separation tank 8 and liquid hydrocarbon washing water booster pump 38；After removal of mercaptans, liquid hydrocarbon can be entrained with trace alkali liquor, alkali
Property photosynthetic matter accumulation increase after can cause liquid hydrocarbon deep processing device catalyst poisoning, therefore after alkali cleaning liquid hydrocarbon need design washing
Dealkalize；The liquid hydrocarbon flowed out from caustic wash desulfuration alcohol unit C1 with from liquid hydrocarbon washing water booster pump 38 demineralized water or soft out
Change water to mix through liquid hydrocarbon venturi mixer 13, in the alkali dose carried secretly to water and at liquid hydrocarbon, wash settlement separation tank 7
Separating, alkaline water periodic exhaustion goes out device, supplements the fresh demineralized water of equivalent simultaneously or softens water；It is typically designed one-level liquid hydrocarbon
Washing fiber liquid film contact, can control liquid hydrocarbon neutral and alkali material at below 0.1ppm by controlling the replacing desalination water yield.
Extractive distillation disulfide unit E includes that abstraction desulfurization agent tank 14, abstraction desulfurization agent dosing pump 39, abstraction desulfurization agent mix
Clutch 15, extraction distillation column 16, extraction distillation column liftout cooler 18, extraction distillation column liftout return tank 19, extraction distillation column
Liftout reflux pump 40, reboiler 20 and extraction distillation column bed material cooler 21, extraction distillation column 16 is equipped with column plate 2 17；For containing
There is the liquid hydrocarbon feeds of disulfide, use distillation column abstraction desulfurization agent removal methods；The liquid hydrocarbon flowed out from washing dealkalize cells D
After abstraction desulfurization agent blender 15 mixes, extractive distillation is entered with the abstraction desulfurization agent sent by abstraction desulfurization agent dosing pump 39
Tower 16, extraction distillation column 16 operates pressure and enters device liquid hydrocarbon pressure and upstream desulphurization plant pressure drop decision, tower top pressure one
As in 0.3-2.2MPa scope, tower bottom pressure is typically in 0.4-2.3MPa scope, and tower bed material part is heated back to through reboiler 20
Extraction distillation column 16,60-140 DEG C of scope bottom control tower point, overhead reflux ratio is for 0.3-0.9, and reflux temperature is 40-50 DEG C
Scope, tower top temperature controls 50-70 DEG C of scope；Abstraction desulfurization agent addition is the 300-1000ppm of liquid hydrocarbon mass flow,
Improve abstraction desulfurization agent addition and can reduce overhead reflux ratio, reduce extractive distillation desulfurization energy consumption and operating cost, also can improve
Disulfide removal efficiency；In liquid hydrocarbon, disulfide content can be removed to below 5ppm, and in catalytic liquid activating QI, disulfide content can reach
Below 1ppm；Sulfur-bearing at the bottom of tower gives up agent carrying device after cooling, can mix gasoline or diesel oil carries out hydrodesulfurization process.
Adsorbent desulfurization unit F includes adsorbing desulfurizing tower 22, and absorption desulfurizing tower 22 is built with modified molecular screen 23；From extraction
The Liquefied Hydrocarbon flowed out in distillation disulfide unit E, catalytic liquid activating QI total sulfur can reach below 3ppm, coking liquefied gas and other liquid
State hydrocarbon total sulfur can reach below 10ppm；For the operating mode of higher desulfurization demand, then use adsorption tower modified molecular screen adsorbing and removing
Residual sulphur device, the liquid hydrocarbon after extractive distillation desulfurization, from tower bottom enter adsorption tower, adsorption tower built with modified molecular screen,
Modified molecular screen is the 13x molecular sieve through rare earth element modification by calcination, and modified molecular screen Sulfur capacity reaches 1.5%, adsorption tower air speed
For 0.5-3, adsorption tower ratio of height to diameter is 5-15, and liquid hydrocarbon total sulfur can be removed to below 1ppm.Molecular sieve after desulfurization absorption is saturated
Factory's regeneration can be returned reuse.
Following embodiment all uses TS-2000 type sulfur determinator to analyze total sulfur, uses 9790 type chromatographic
Sulfur speciation, uses atomic absorption spectrography (AAS) detection alkaline matter content, and SH T 0233-92 liquefied petroleum gas is pressed in liquid hydrocarbon sampling
Sampling method performs:
Embodiment 1: certain plant catalytic liquefied gas temperature 30-40 DEG C, pressure 2.4-2.5MPa, hydrogen sulfide content 15000-
30000mg/Nm3, mercaptans content 300-500mg/Nm3, COS content 10-15mg/Nm3, disulfide content 5-10mg/Nm3,
Other Sulfur total content 5-10mg/Nm3, it is desirable to liquefied refinery gas total sulfur content is less than 1mg/Nm3, sodium ions content is less than
0.1ppm。
Using two-stage fiber film contactor amine eluting hydrogen sulfide, in de-rear liquefied gas, hydrogen sulfide content is less than 10mg/
Nm3；Use the carbonyl sulfide hydrolysis of one-level and absorb hydrogen sulfide unit B 1 and carbonyl sulfide removal agent regeneration unit B2, rich carbonyl
Sulfur scavenger regenerant flow is the 15% of circular flow, and in de-rear liquefied gas, hydrogen sulfide content is less than 1 mg/Nm3, COS content
Less than 1 mg/Nm3；Use caustic wash desulfuration alcohol unit C1, alkali liquor oxidized unit C2, alkali liquor back suction stripping unit C3 and the solvent of two-stage
Washing unit C4, sulfonation titanium cyanines cobalt content 100-150ppm in system alkali liquor, oxidizing tower alkali liquid temperature at 50-65 DEG C, oxidizing tower
Operation pressure 0.1-0.2MPa, enters device back suction and carries gasoline total sulfur less than 10ppm, and in regeneration alkali liquor, sodium mercaptides concentration is less than
50ppm, disulfide concentration are less than 10ppm, and in de-rear liquefied gas, mercaptans content is less than 2 mg/Nm3；One-level fiber liquid film is used to connect
Tentaculum washing dealkalize cells D, after washing, in liquefied gas, sodium ions content is less than 0.1ppm；Distillation extraction tower is used to remove two sulfur
Ether, distillation column pressure on top surface is typically in 2.1-2.2MPa scope, and tower bottom pressure is typically at 2.2-2.3MPa scope, tower bed material part warp
Reboiler is heated back to extraction distillation column, and 130-140 DEG C of scope bottom control tower point, overhead reflux ratio is for 0.8-0.9, backflow
Temperature is 40-50 DEG C of scope, and tower top temperature controls 60-70 DEG C of scope, and abstraction desulfurization agent addition is liquid hydrocarbon mass flow
300-400ppm, de-after in liquefied gas disulfide content less than 3mg/Nm3；Use adsorption tower modified molecular screen removing residual
Sulfur, adsorption tower air speed is 3, and adsorption tower ratio of height to diameter is 5；After de-, liquefied gas total sulfur is less than 3 mg/Nm3, the every finger of liquefied refinery gas
Mark reaches to design requirement.
Embodiment 2: certain refinery's coking liquefied gas temperature 30-45 DEG C, pressure 1.4-1.6MPa, hydrogen sulfide content 35000-
60000mg/Nm3, mercaptans content 3000-6000mg/Nm3, COS content 20-30mg/Nm3, disulfide content 50-80mg/
Nm3, other Sulfur total content 20-50mg/Nm3, it is desirable to liquefied refinery gas total sulfur content is less than 100mg/Nm3, copper corruption detects
1 grade, sodium ions content is less than 1ppm.
Using two-stage fiber film contactor amine eluting hydrogen sulfide, in de-rear liquefied gas, hydrogen sulfide content is less than 20mg/
Nm3；Use the carbonyl sulfide hydrolysis of one-level fiber film contactor and absorb hydrogen sulfide unit B 1 and carbonyl sulfide removal agent regeneration
Unit B 2, rich carbonyl sulfide removal agent regenerant flow is the 20% of circular flow, and in de-rear liquefied gas, hydrogen sulfide content is less than 1 mg/
Nm3, COS content is less than 1 mg/Nm3；Use the caustic wash desulfuration alcohol unit C1 of two-stage fiber film contactor, alkali liquor oxidized list
Unit C2, alkali liquor back suction stripping unit C3 and solvent washing unit C4, sulfonation titanium cyanines cobalt content 150-200ppm in system alkali liquor, oxidation
Tower alkali liquid temperature at 30-45 DEG C, oxidizing tower operation pressure 0.5-0.6MPa, enter device back suction and carry gasoline total sulfur less than 10ppm, then
In raw alkali liquor, sodium mercaptides concentration is less than 100ppm, disulfide concentration less than 50ppm, and in de-rear liquefied gas, mercaptans content is less than
10mg/Nm3；Using one-level fiber film contactor washing dealkalize cells D, after washing, in liquefied gas, sodium ions content is less than
1ppm；Using distillation extraction tower removing disulfide, distillation column pressure on top surface is typically in 1.1-1.3MPa scope, and tower bottom pressure typically exists
1.2-1.4MPa scope, tower bed material part is heated back to extraction distillation column through reboiler, divides at 110-120 DEG C of model bottom control tower
Enclosing, overhead reflux ratio is for 0.5-0.6, and reflux temperature is 40-50 DEG C of scope, and tower top temperature controls 60-70 DEG C of scope, and extraction is de-
Sulfur agent addition is the 400-500ppm of liquid hydrocarbon mass flow, and in de-rear liquefied gas, disulfide content is less than 5mg/Nm3；Do not set
Meter adsorption tower modified molecular screen removing residual sulphur；Liquefied gas total sulfur 70-80mg/Nm after de-3, liquefied refinery gas indices reaches
Design requirement.
Embodiment 3: carbon four temperature 50-60 DEG C after certain refinery's edema caused by disorder of QI, pressure 0.5-0.6MPa, hydrogen sulfide content is less than 1mg/
Nm3, mercaptans content 50-80mg/Nm3, COS content is less than 1mg/Nm3, disulfide content 150-200mg/Nm3, other form
Sulfur total content 30-50mg/Nm3, it is desirable to refining carbon four total sulfur content is less than 5mg/Nm3, copper corruption detects 1 grade, and sodium ions content is little
In 1ppm.
Use the caustic wash desulfuration alcohol unit C1 of one-level fiber film contactor, alkali liquor oxidized unit C2, the alkali liquor back suction bill of lading
Unit C3 and solvent washing unit C4, sulfonation titanium cyanines cobalt content 100-120ppm in system alkali liquor, oxidizing tower alkali liquid temperature is at 40-50
DEG C, oxidizing tower operation pressure 0.2-0.3MPa, enter device back suction and carry gasoline total sulfur less than 10ppm, in regeneration alkali liquor, sodium mercaptides is dense
Degree is less than 10ppm, disulfide concentration less than 50ppm, and in de-rear carbon four, mercaptans content is less than 3mg/Nm3；Use one-level fiber liquid
Membrane contactor washing dealkalize unit, after washing, in carbon four, sodium ions content is less than 1ppm；Use distillation extraction tower removing disulfide,
Distillation column pressure on top surface is typically in 0.3-0.4MPa scope, and tower bottom pressure is typically in 0.4-0.5MPa scope, and tower bed material part is through again
Boiling device is heated back to extraction distillation column, and 60-70 DEG C of scope bottom control tower point, overhead reflux ratio is for 0.3-0.4, reflux temperature
For 40-50 DEG C of scope, tower top temperature controls 50-55 DEG C of scope, and abstraction desulfurization agent addition is the 500-of carbon four mass flow
600ppm, in de-rear carbon four, disulfide content is less than 3mg/Nm3；Use adsorption tower modified molecular screen removing residual sulphur, adsorption tower
Air speed is 1, and adsorption tower ratio of height to diameter is 10；Carbon four total sulfur 2-5mg/Nm after de-3.Refining carbon four indices reaches to design requirement.
Embodiment 4: certain refinery's outsourcing mixing carbon four temperature 10-30 DEG C, pressure 0.5-0.6MPa, hydrogen sulfide content is less than
1mg/Nm3, mercaptans content 100-200mg/Nm3, COS content is less than 1mg/Nm3, disulfide content 200-500mg/Nm3, its
Its Sulfur total content 50-100mg/Nm3, it is desirable to refining carbon four total sulfur content is less than 5mg/Nm3, copper corruption detect 1 grade, sodium from
Sub-content is less than 1ppm.
Use the caustic wash desulfuration alcohol unit C1 of two-stage fiber film contactor, alkali liquor oxidized unit C2, the alkali liquor back suction bill of lading
Unit C3 and solvent washing unit C4, sulfonation titanium cyanines cobalt content 120-150ppm in system alkali liquor, oxidizing tower alkali liquid temperature is at 40-50
DEG C, oxidizing tower operation pressure 0.3-0.4MPa, enter device back suction and carry gasoline total sulfur less than 10ppm, in regeneration alkali liquor, sodium mercaptides is dense
Degree is less than 10ppm, disulfide concentration less than 50ppm, and in de-rear carbon four, mercaptans content is less than 2mg/Nm3；Use one-level fiber liquid
Membrane contactor washing dealkalize unit, after washing, in carbon four, sodium ions content is less than 1ppm；Use distillation extraction tower removing disulfide,
Distillation column pressure on top surface is typically in 0.3-0.4MPa scope, and tower bottom pressure is typically in 0.4-0.5MPa scope, and tower bed material part is through again
Boiling device is heated back to extraction distillation column, and 60-70 DEG C of scope bottom control tower point, overhead reflux ratio is for 0.3-0.4, reflux temperature
For 40-50 DEG C of scope, tower top temperature controls 50-55 DEG C of scope, and abstraction desulfurization agent addition is the 800-of carbon four mass flow
1000ppm, in de-rear carbon four, disulfide content is less than 10mg/Nm3；Use adsorption tower modified molecular screen removing residual sulphur, absorption
Tower air speed is 0.5, and adsorption tower ratio of height to diameter is 15；Carbon four total sulfur 2-5mg/Nm after de-3, refining carbon four indices reaches design to be wanted
Ask.
Embodiment 5: propylene temperature 30-45 DEG C after certain refinery's edema caused by disorder of QI, pressure 1.6-1.8MPa, hydrogen sulfide content is less than 5mg/
Nm3, COS content 20-70mg/Nm3, it is desirable to refined propylene total sulfur content is less than 1mg/Nm3。
Use the carbonyl sulfide hydrolysis of one-level fiber film contactor and absorb hydrogen sulfide unit B 1 and carbonyl sulfide removal agent
Regeneration unit B2, rich carbonyl sulfide removal agent regenerant flow is the 30% of circular flow.After de-, in propylene, hydrogen sulfide content does not measures,
COS content is less than 1 mg/Nm3, total sulfur content is less than 1 mg/Nm3。
Embodiment 6: certain refinery's outsourcing mixing carbon five temperature 10-30 DEG C, pressure 0.5-0.6MPa, hydrogen sulfide content is less than
1mg/Nm3, mercaptans content 200-300mg/Nm3, COS content is less than 1mg/Nm3, disulfide content 20-40mg/Nm3, other
Sulfur total content 50-80mg/Nm3, it is desirable to refining carbon five total sulfur content is less than 10mg/Nm3, copper corruption detects 1 grade, sodium ion
Content is less than 1ppm.
Use the caustic wash desulfuration alcohol unit C1 of two-stage fiber film contactor, alkali liquor oxidized unit C2, the alkali liquor back suction bill of lading
Unit C3 and solvent washing unit C4, sulfonation titanium cyanines cobalt content 100-120ppm in system alkali liquor, oxidizing tower alkali liquid temperature is at 40-50
DEG C, oxidizing tower operation pressure 0.3-0.4MPa, enter device back suction and carry gasoline total sulfur less than 10ppm, in regeneration alkali liquor, sodium mercaptides is dense
Degree is less than 10ppm, disulfide concentration less than 50ppm, and in de-rear carbon four, mercaptans content is less than 2mg/Nm3；Use one-level fiber liquid
Membrane contactor washing dealkalize unit, after washing, in carbon four, sodium ions content is less than 1ppm；Use distillation extraction tower removing disulfide,
Distillation column pressure on top surface is typically in 0.3-0.4MPa scope, and tower bottom pressure is typically in 0.4-0.5MPa scope, and tower bed material part is through again
Boiling device is heated back to extraction distillation column, and 60-70 DEG C of scope bottom control tower point, overhead reflux ratio is for 0.7-0.8, reflux temperature
For 40-50 DEG C of scope, tower top temperature controls 50-55 DEG C of scope, and abstraction desulfurization agent addition is the 300-of carbon four mass flow
400ppm, in de-rear carbon four, disulfide content is less than 3mg/Nm3；Use adsorption tower modified molecular screen removing residual sulphur, adsorption tower
Air speed is 1.5, and adsorption tower ratio of height to diameter is 12；Carbon four total sulfur 5-8mg/Nm after de-3, refining carbon five mass reaches design objective and wants
Ask.
Embodiment 7: the saturated liquefied gas temperature in certain refinery 30-40 DEG C, pressure 1.4-1.6MPa, hydrogen sulfide content 5000-
8000mg/Nm3, mercaptans content 300-500mg/Nm3, COS content 10-20mg/Nm3, disulfide content 20-30mg/Nm3,
Other Sulfur total content 20-50mg/Nm3, it is desirable to liquefied refinery gas total sulfur content is less than 200mg/Nm3, copper corruption detects 1 grade,
Sodium ions content is less than 1ppm.
Using one-level fiber film contactor amine eluting hydrogen sulfide, in de-rear liquefied gas, hydrogen sulfide content is less than 10mg/
Nm3；Use the carbonyl sulfide hydrolysis of one-level fiber film contactor and absorb hydrogen sulfide unit B 1 and carbonyl sulfide removal agent regeneration
Unit B 2, rich carbonyl sulfide removal agent regenerant flow is the 15% of circular flow, and in de-rear liquefied gas, hydrogen sulfide content is less than 1 mg/
Nm3, COS content is less than 1 mg/Nm3；Use the caustic wash desulfuration alcohol unit C1 of two-stage fiber film contactor, alkali liquor oxidized list
Unit C2, alkali liquor back suction stripping unit C3 and solvent washing unit C4, sulfonation titanium cyanines cobalt content 100-150ppm, oxygen in system alkali liquor
Change tower alkali liquid temperature at 50-65 DEG C, oxidizing tower operation pressure 0.3-0.4MPa, enter device back suction and carry gasoline total sulfur less than 10ppm,
In regeneration alkali liquor, sodium mercaptides concentration is less than 100ppm, disulfide concentration less than 100ppm, and in de-rear liquefied gas, mercaptans content is less than 3
mg/Nm3；Using one-level fiber film contactor washing dealkalize unit, after washing, in liquefied gas, sodium ions content is less than 1ppm；Not
Design distillation extraction tower removing disulfide and modified molecular screen adsorption tower removing residual sulphur；Liquefied gas total sulfur 50-120 mg/ after de-
Nm3, liquefied refinery gas indices reaches to design requirement.
Claims (6)
1. a device for liquid hydrocarbon fine de-sulfur, including the amine eluting sulfur of the hydrogen sulfide added in MDEA lean amine absorption liquid hydrocarbon
Change hydrogen unit (A), the rich carbonyl sulfide removal agent of addition carries out the carbonyl sulfide hydrolysis of decarbonylation base sulphuring treatment and absorbs sulfuration liquid hydrocarbon
Hydrogen unit (B1), addition regeneration alkali liquor carry out caustic wash desulfuration alcohol unit (C1) of de-disulfide, carry out liquid hydrocarbon liquid hydrocarbon
Wash extractive distillation disulfide unit (E) of the disulfide in washing dealkalize unit (D) of dealkalize, removing liquid hydrocarbon and be used for extracting
Taking the adsorbent desulfurization unit (F) of the liquid hydrocarbon after distillation desulfurization, pending liquid hydrocarbon flows through said apparatus successively；
Described amine eluting hydrogen sulfide unit (A) includes depriving hydrogen sulphide fiber film contactor (1) and amine liquid settlement separation tank (2),
Described depriving hydrogen sulphide fiber film contactor (1) is circumscribed with pending liquid hydrocarbon pipe (a1) and MDEA lean amine liquid pipe (a2)；
Described carbonyl sulfide hydrolysis and absorption hydrogen sulfide unit (B1) include that de-cos venturi mixer (12), de-cos are fine
Dimension liquid membrane contactor (3) and carbonyl sulfide removal agent settlement separation tank (4)；Described de-cos venturi mixer (12) is with described
Amine liquid settlement separation tank (2) docks, and side joint has rich carbonyl sulfide removal agent pipe (b1), described carbonyl sulfide removal agent settlement separation tank
(4) bottom is provided with lean carbonyl sulfide removal agent pipe (b2)；
Described caustic wash desulfuration alcohol unit (C1) includes removal of mercaptans fiber film contactor (5) and alkali liquor settlement separation tank (6), described
Removal of mercaptans fiber film contactor (5) docks with described carbonyl sulfide removal agent settlement separation tank (4), and side joint has regeneration alkali liquor pipe
(c1)；The bottom of described alkali liquor settlement separation tank (6) is provided with alkali liquor oxidized pipe (c2)；
Described washing dealkalize unit (D) includes the washing fiber liquid film contact of liquid hydrocarbon washing venturi mixer (13), liquid hydrocarbon
Device (7), liquid hydrocarbon washing settlement separation tank (8) and liquid hydrocarbon washing water booster pump (38)；Described liquid hydrocarbon washing venturi mixes
Clutch (13) is docked with described alkali liquor settlement separation tank (6)；
Described extractive distillation disulfide unit (E) includes that abstraction desulfurization agent tank (14), abstraction desulfurization agent dosing pump (39), extraction take off
Sulfur agent blender (15), extraction distillation column (16), extraction distillation column liftout cooler (18), extraction distillation column liftout return tank
(19), extraction distillation column liftout reflux pump (40), reboiler (20) and extraction distillation column bed material cooler (21), described extraction steaming
Evaporate tower (16) to dock with liquid hydrocarbon washing settlement separation tank (8) equipped with column plate two (17), described abstraction desulfurization agent blender (15)；
Described adsorbent desulfurization unit (F) includes adsorbing desulfurizing tower (22), and described absorption desulfurizing tower (22) is built with modified molecules
Sieve (23), described absorption desulfurizing tower (22) is docked with described extraction distillation column liftout reflux pump (40)；
It is characterized in that: be additionally provided with carbonyl sulfide removal agent regeneration unit (B2) that rich carbonyl sulfide removal agent recycling is processed,
Described carbonyl sulfide removal agent regeneration unit (B2) includes rich carbonyl sulfide removal agent regenerator (24), tower top material reflux pump (45), tower
Liftout return tank (27), tower bed material cooler (28) and lean carbonyl sulfide removal agent booster pump (41)；Described rich carbonyl sulfide removal agent
Regenerator (24) is built with column plate one (25) and heating coil (26), and described lean carbonyl sulfide removal agent pipe (b2) is docked at rich carbonyl
On sulfur scavenger regenerator (24), described rich carbonyl sulfide removal agent pipe (b1) is docked at described lean carbonyl sulfide removal agent booster pump
(41) on.
The device of a kind of liquid hydrocarbon fine de-sulfur the most as claimed in claim 1, it is characterised in that: also include adding air to alkali liquor
Carrying out the alkali liquor oxidized unit (C2) aoxidized, described alkali liquor oxidized unit (C2) includes that alkali liquor preheater (29), catalyst inject
Device (30), air and liquid mixer (31) and alkali liquor filler oxidizing tower (32)；Described air and liquid mixer (31) is circumscribed with compressed air hose
(c3), be disposed with from bottom to top in described alkali liquor filler oxidizing tower (32) gas-liquid allotter (35), filler (34) and L-type every
Plate (33), is circumscribed with alkali liquor washing pipe (c4) at the region that described L-type dividing plate (33) is divided into；Described alkali liquor oxidized pipe (c2), institute
State alkali liquor preheater (29), described air and liquid mixer (31) and described gas-liquid allotter (35) to be sequentially connected.
The device of a kind of liquid hydrocarbon fine de-sulfur the most as claimed in claim 2, it is characterised in that: offer regeneration alkali liquor is also provided
Alkali liquor back suction stripping unit (C3), described alkali liquor back suction stripping unit (C3) include back suction carry fiber film contactor (9), oil alkali deposited
Fall knockout drum (10), regenerating alkali liquid pump (42) and solvent circulating pump (43), be provided with in described oily alkali settlement separation tank (10) every
Plate (11)；Described back suction carries fiber film contactor (9) and docks with described alkali liquor washing pipe (c4), described regenerating alkali liquid pump (42)
Dock with described regeneration alkali liquor pipe (c1).
The device of a kind of liquid hydrocarbon fine de-sulfur the most as claimed in claim 3, it is characterised in that: also include addition water and process
Sulfur-bearing solvent solvent washing unit (C4), described solvent washing unit (C4) include solvent washing venturi mixer (36),
Solvent washing settlement separation tank (37) and aqueous solvent wash water booster pump (44)；Described solvent washing venturi mixer (36) and institute
State solvent circulating pump (43) docking.
The device of a kind of liquid hydrocarbon fine de-sulfur the most as claimed in claim 1, it is characterised in that: described modified molecular screen (23) changes
Property molecular sieve is the 13x molecular sieve through rare earth element modification by calcination.
The device of a kind of liquid hydrocarbon fine de-sulfur the most as claimed in claim 2, it is characterised in that: described filler (34) porcelain ball, Bao
That ring, Raschig ring, ripple packing or wire packing；Regular windrow or scattered windrow can be used.
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